Oil additive concentrate



3,058,910 01L ADDITIVE CONCENTRATE Thaddeus W. Culrner, Robinson, Ill., assignor to Hall Stewart, Danville, Ill. N Drawing. Filed (let. 24, 1958, Ser. No. 769,308 5 Claims. Cl. 252-32..7)

This invention relates to an oil additive concentrate, and is a continuation in part of my application 498,443, filed March 31, 1955, now abandoned.

The oil additive concentrate of this invention comprises a mixture of the addition product of an alkylene polyamine and a dithiophosphoric acid ester in combination with another addition product of an organic sulfonic acid and an amine. The dithiophosphoric acid ester addition product acts as a corrosion inhibitor when added to a hydrocarbon lubricant while the organic sulfonic acid addition product acts as a detergent and an antiacid. If desired, the corrosion inhibitor of this invention may be used in a lubricant alone or with another detergent and, similarly, the detergent of this invention may be used alone in a lubricant or with another inhibitor.

The oil additives of this invention have a number of new and unobvious advantages not obtained by the prior additives. Thus the additive, when added to a hydrocarbon lubricant such as' a hydrocarbon oil, results in a lower coefficient of friction between the metallic parts lubricated by the oil. Furthermore, the additive of this invention permits oil coating and lubricating of a surface even when this surface is in contact with water. An oil containing the additive concentrate of this invention does not get destructively acid even over long periods of time and when subjected to extreme wear and high temperatures. Thus, actual tests have shown that the oil in use has a slight drop in pH value 'but this value then remains constant at a safe level for extremely long periods of time. The oil containing the subject additive concentrate does not corrode metal surfaces and aids in the lubrication of these surfaces.

One of the very important advantages of the additives of this invention is that they are ashless. By ashless is meant an oil additive which does not break down and furnish metal derivatives to the host oil which in turn may be more or less abrasive and cause wear. This beneficial result is obtained by providing an additive concentrate which contains no metallic components. Any deposits formed in engines lubricated with lubricants and oils containing the subject additive concentrates are minimized since there are no metallic elements to serve as a nucleus for the concentration of carbon deposits, even when the oils are subjected to excessive service and high temperatures.

The principal object of this invention therefore is to provide an improved oil additive and an improved lubricating composition, each of the type discussed above and and having the above described new and unobvious vantages.

The inhibitor of this invention is the addition product of an alkylene polyamine and a dithiophosphoric acid ester. lThis ester has essentially the following formula The preferred substituted phenol with an aliphatic side chain is known as a nonyl phenol whose structural formula is:

ice

Although it has been determined that octyl phenol will operate satisfactorily or other substituted phenols with fewer carbon atoms, the solubility of the additive concentrate is substantially reduced with those compounds of lesser carbon side chains than nonyl phenol. Similarly it has been determined that decyl phenol and high carbon atom side chains will perform satisfactorily, but the congealing properties increase quite rapidly with side chains longer than the preferred nonyl phenol.

The above substituted phenol ester may be prepared by reacting phosphorus pentasulfide with the corresponding alcohol in the proportions of at least 4 mols of the alcohol per 1 mol ofhosphorus pentasulfide. The product may be produced by refluxing this mixture until all of the pentasulfide is dissolved and then purging hydrogen sulfide from the system.

The dithiophosphoric acid ester, as described above, is reacted with an alkylene polyam-ine to form an addition product which is the inhibitor. The polyamines which may be employed are alkylene polyamines such as ethylene diamine, diethylene triamine, triethylene tetraamine, tetraethylene pentamine, tetramethyl methylene diamine, propylene di 'ne, dipropylene triamine, tripropylene tetramine, N-n-dodecyl diethylene triamine, N- octyl ethylene diamine, hydroethylethylene diamine, hydroxy isopropyl propylene diamine, hydroxy ethyl diethylene triamine, N beta-hydroxypropyl propylene diamine, N-n-hexadecyl diethylene triamine, 3-diethyl amino propylamine, 1,3-diamine butane, 1,10-decylene diamine, phenyl ethylene diamine, di-o-tolyl ethylene diamine and the like. 'Ihe preferred polyamines are those having at least one hydrogen atom on each nitrogen atom.

The detergent of this invention is formed from the addition product of an amine and an organic sulfonic acid. Sulfonic acids which may be used to make the detergent-s of this invention include petroleum sulfonic acids such as mahogany sulfonic acids; petrolatum sulfonic acids; monoand polywax substituted naphthalene sulfonic, phenol sulfonic, diphenyl ether sulfonic, diphenyl ether disulfonic, naphthalene disulfide sulfonic, naphthalene disulfide disulfonic, diphenyl amine disulfonic, diphenyl amine sulfonic, thiophene sulfonic, alpha-chloronaphthalene sulfonic acids, etc.; other substituted sulfonic acids such as cetyl chlorobenzene sulfonic acids, cetylphenol sulfonic acids, octyl-phenol disulfide sulfonic acids, cetyl-phenol monosulfide sulfonic acids, cetoxy caprylbenzene sulfonic acids, di-cetyl thianthrene sulfonic acids, di-lauryl beta-naphthol sulf-onic acids, and di-capryl nitronaphthalene sulfonic acids; aliphatic sulfonic acids such as parafiin wax \sulfonic acids, unsaturated paraflin wax sulfonic acids, hydroxy substituted paraflin wax sulfonic acids, tetraisobutylene sulfonic acids, tetra-amylene sulfonic acids, chloro-substituted paraffin wax sulfonic acids, nitroso parafiin wax sulfonic acids, etc.; cycloaliphatic sulfonic acids, such as petroleum naphthene sulfonic acids, cetyl-cyclopentyl sulfonic acids, lauryl-cyclo-hexyl sulfonic acids, bix-(diisobutyl)-cyclohexyl sulfonic acids, monoand poly-wax substituted cyclo-hexy-l sulfonic acids and the like.

The term petroleum sul-fonic acids used herein is in tended to include all sulfonic acids that are derived from petroleum products.

The amine used to form the addition product with the organic sulfonic acid is preferably an amine having at least 1 hydrogen atom on a nitrogen atom. Thus the preferred amines are either primary or secondary amines, especially preferred amines are the alkylene polyamines described above in connection with the dithiophosphate inhibitor.

water solubility of at least about and detergent it is preferred that a concentrate dissolved in the oil.

The preferred organic sulfonic acid is one having a 0.0005 by weight at C., a pH of less than 7 in an aqueous solution at 25 C. and an ionization constant in water of at least 1 10- at 25 C.

In preparing the mixed inhibitor and detergent the same polyamine used in making the detergent may be used in making the inhibitor by merely using an ex a temperature of 50 'cess of the amine in the detergent and reacting this excess with dithiophosphoric acid ester to make the mixed detergent and inhibitor. This can be done by adding the dithiophosphate ester to the mixture of detergent and excess alkylene diamine.

In making the oil additive from the mixed inhibitor be produced containing from about 0.5-25% by weight of the inhibitor and about 10-80% by weight of the detergent with any additional concentrate being made up with a required percentage of a iight hydrocarbon oil. This concentrate may then be added to a hydrocarbon lubricating oil in an amount up to about 20% by weight of the finished lubricating composition. As a practical matter, the lower amount of concentrate may be about 0.05% by weight.

'Thus in this composition the detergent may be used alone or with the inhibitor of this invention or another inhibitor or the inhibitor may be used alone or in combination with this detergent or another detergent. In any case, superior lubricants are produced.

In the preferred instances, the polyamine used to make the inhibitor and preferably used in producing the detergent preferably contains from 2-20 carbon atoms in the molecule. diamine having at least 1 hydrogen atom on each nitrogen atom. The sulfonic acid used in producing the detergent preferably contains at least about 18-24. carbon atoms in the molecule in order to assure good oil solubility. The preferred sulfonic acid is a petroleum sulfonic acid.

In one method of producing a combined inhibitor and detergent according to this invention a mixture of about 62% by Weight of petroleum sodium sulfonate in mineral ,oil was diluted with about an equal weight of 100 100 pale hydrocarbon oil. An amount of hydrochloric acid substantially molecular-1y in slight excess equivalent to the amount of sodium sulfon-ate was then added to convert the sulfonate to petroleum sulfonic acid. Moderate heat and agitation accelreate the reaction and aid separation. The resulting sodium chloride and excess hydrochloric acid separated from the solution and was removed. The remaining liquid was essentially petroleum sulfonic acid This is the Well known manner of producing petroleum sulfonic acid. If desired, it can also be produced by treating a petroleum oil with fuming sulphuric acid or with chlorosulfonic acid.

To the above produced petroleum sulfonic acid dissolved in oil was then added an amount of ethylene diamine sufficient to neutralize the acid and produce at least a 2 mol excess of the ethylene diamine. The resulting product consisted essentially of the oil having distributed therethrough the addition product of ethylene diamine and petroleum sulfonic acid with an excess of ethyl ene diamine. This addition produce is the detergent of the inhibitor.

To produce the corrosion inhibitor concentrate 5 mols of nonyl phenol were mixed with .1 mol of phosphorus pentasulfide. The mixture was refluxed at a temperature 'of about 100 C. until all of the phosphorus pentasulfide of ethylene diamine and the petroleum sodium sul-' In the preferred instance, this polyamine is a .butane diamine, and (2) fonate. The ester then formed the addition product with the excess ethylene diamine which constitutes the inhibitor.

In one example of an additive prepared according to this invention the additive contained about 52.3% by weight of petroleum sulfonic acid in a 50-50% by Weight mixture of the additive and a hydrocarbon oil, about 5.3% by weight of ethylene diamine, about 5.4% by weight of the nonyl phenol ester of dithiophosphoric acid and about 57% by weight of 100 100 hydrocarbon oil. This additive which was in the form of a concentrate, in an amount of about 2 to 20% by volume, was added to a hydrocarbon engine lubricating oil.

In the event the additive of this invention is prepared with a one or more mol excess of ethylene diamine, a clear solution does not result in oil. If a clear solution is desired, 5-20% by weight of the additive of a high boiling oil soluble alcohol such as amyl, hexyl, octyl and nonyl alcohols or an oil soluble'alkyl substituted phenol such as nonyl phenol may be added to clear up any hazy appearance.

Having described my invention as related to the embodiments set out herein, it is my intention that the invention be not limited by any of the details of description unless otherwise specified, but rather be construed broadly within its spirit and scope as set out in the accompanying claims.

I claim:

1. An additive concentrate for addition to a lubricating oil'in an amount in the range of about 0.05 to 20 percent by weight consisting essentially of a hydrocarbon of about 0.5 to 25 wt. percent, based on concentrate, of the oil-soluble addition product of the acid thiophosphate ester of nonyl phenol and phosphorus pentasulfide with an alkylene diamine, and (2) in the range of about 10 to wt. percent, based on concentrate, of the oil-soluble addition product of a petroleum sulfonic acid having from 18 to 24 carbon atoms per molecule and an alkylene diamine, in each instance said alkylene diamine being class consisting of ethylene diamine, propylene diamine and butane diamine.

2. additive concentrate for addition to a lubricatmg 0 in an amount in the range of about 0.05 to 20 by weight consisting essentially of a hydrocarbon 80 percent, based on concentrate, of'the oil-soluble addition product of a petroleum sulfonic acid having from 18 to 24 carbon atoms per molecule. and ethylene diamine.

3. additive concentrate for addition to a lubricatmg 011 in an amount in the range of about 0.05 to 20 percent by weight consisting essentially of a hydrocarbon 80 wt. percent, based on concentrate, addition product of a ene diamine. 4. An additive concentrate for addition to a lubricatmg oil in an amount in the range of about 0.05 to 20 percent by weight consisting essentially of a hydrocarbon lubricating oil containing a mixture of (1) in the range of about 0.5 to 25 wt. percent, based on concentrate, of the oil-soluble addition product of the acid thiophosphate ester of nonyl phenol and phosphorus pentasulfide with in the range of about 10 to 80 wt. percent, based on concentrate, of the oil-solubleaddi {of the oil-soluble petroleum sulfonic acid and propyltion product of a petroleum sulfonic acid and butane diamine.

5. An additive concentrate for addition to a lubricating oil in an amount in the range of about 0.05 to 20 percent by weight consisting essentially of a hydrocarbon lubricating oil having a viscosity of about 100 SUS at 100 F. containing a mixture of (l) in the range of about 0.5 to 25 Wt. percent, based on concentrate, of the oil-soluble addition product of the acid thiophosphate ester of nonyl phenol and phosphorus pentasulfide with ethylene diamine, and (2) in the range of about 10 to 80 wt. percent, based on concentrate, of the oil-soluble addition product of a petroleum sulfonic acid having fiom 18 to 24 carbon atoms per molecule and ethylene diamine, said sulfonic acid having a Water solubility of at least about 0.0005% by weight at a temperature of 50 C.,

a pH of less than 7 in an aqueous solution at 25 C.

and an ionization constant in water of at least 1X10 at 25 C.

References Cited in the file of this patent UNITED STATES PATENTS Benning Aug. 1, 1939 Musselman Apr. 30, 1946 Lewis Mar. 25, 1947 Zimmer Jan. 15, 1952 Hill July 7, 1953 Buck et a1 July 2, 1957 Alford et a1. Oct. 15, 1957 Fortune Jan. 7, 1958 Millikan July 14, 1959 

1. AN ADDITIVE CONCENTRATE FOR ADDITION TO A LUBRICATING OIL IN AN AMOUNT IN THE RANGE OF ABOUT 0.05 TO 20 PERCENT BY WEIGHT CONSISTING ESSENTIALLY OF A HYDROCARBON LUBRICATING OIL CONTAINING A MIXTURE OF (1) IN THE RANGE OF ABOUT 0.5 TO 25 WT. PERCENT, BASED ON CONCENTRATE, OF THE OIL-SOLUBLE ADDITION PRODUCT OF THE ACID THIOPHOSPHATE ESTER OF NONYL PHENOL AND PHOSPHORUS PENTASULFIDE WITH AN ALKYLENE DIAMINE, AND (2) IN THE RANGE OF ABOUT 10 TO 80 WT. PERCENT, BASED ON CONCENTRATE, OF THE OIL-SOLUBLE ADDITION PRODUCT OF A PETROLEUM SULFONIC ACID HAVING FROM 18 TO 24 CARBON ATOMS PER MOLECULE AND AN ALKYLENE DIAMINE, IN EACH INSTANCE SAID ALKYLENE DIAMINE BEING SELECTED FROM THE CLASS CONSISTING OF ETHYLENE DIAMINE, PROPYLENE DIAMINE AND BUTANE DIAMINE. 